JPS599634B2 - improved electrolyzer - Google Patents
improved electrolyzerInfo
- Publication number
- JPS599634B2 JPS599634B2 JP49108931A JP10893174A JPS599634B2 JP S599634 B2 JPS599634 B2 JP S599634B2 JP 49108931 A JP49108931 A JP 49108931A JP 10893174 A JP10893174 A JP 10893174A JP S599634 B2 JPS599634 B2 JP S599634B2
- Authority
- JP
- Japan
- Prior art keywords
- anode
- cathode
- diaphragm
- titanium
- electrolytic cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Description
【発明の詳細な説明】 本発明は電解槽における改良に関する。[Detailed description of the invention] The present invention relates to improvements in electrolytic cells.
特に、本発明は被膜形成性金属からなクかつ電気触媒的
に活性な被膜を有す゜陽極を設けた電解槽に関する。In particular, the invention relates to an electrolytic cell having an anode made of a film-forming metal and having an electrocatalytically active coating.
更に本発明はかかる陽極を設けた隔膜槽、特にアルカリ
金属ハロゲン化物の水溶液の電解用隔膜槽に関するもの
である。原理的に、平行に交互に設けられかつ実質的に
垂直な隔膜により相互に分離された一連の陽極と一連の
陰極とからなる隔膜槽は広＜種々のものが知られてり・
る。Furthermore, the present invention relates to a diaphragm tank provided with such an anode, particularly to a diaphragm tank for electrolysis of aqueous solutions of alkali metal halides. In principle, a wide variety of diaphragm vessels are known, consisting of a series of anodes and a series of cathodes arranged alternately in parallel and separated from each other by substantially vertical diaphragms.
Ru.
最近の設計による隔膜槽においては、陽極は適当ｖｃは
被膜形成性金属（通常チタン）からなるプレート状であ
りかつ電気触媒的に活性・ な被膜（例えば白金金属酸
化物）を有し、−ー方陰極は適当には金属（通常軟鋼）
の有孔板又ぱ管状であり、通常陰極の表面上に担持され
るかもしくは該表面に装着される隔膜は適当にはアスベ
スト又は合成有機重合体状物質、例えばポリテトラフッ
ルオロエチレン又はポリ弗化ビニリデンからなる。隔
膜槽の操業に当ク、陽極と陰極との間隔は抵抗損（従つ
て電解摺電圧）を最小限に保つためにできるたけ小さく
して操業することが有利である。同時に、経済的な電流
密度、例えば２Ｌレ省で５ 操業することが望ましい。
しかしながら、高い電流密度と小さい陽極／陰極間隔を
用いた場合には電解中のガス（例えば塩素）の発生速度
が大きくなｖ、これはガスと電解液との気泡を生起し得
る。In diaphragm vessels of recent design, the anode is suitably plate-shaped and composed of a film-forming metal (usually titanium) and has an electrocatalytically active coating (e.g. platinum metal oxide); The polar cathode is suitably made of metal (usually mild steel)
The diaphragm, which is usually in the form of a perforated plate or tube, and which is carried on or attached to the surface of the cathode, is suitably made of asbestos or a synthetic organic polymeric material, such as polytetrafluoroethylene or polyvinylidene fluoride. Become. When operating a diaphragm cell, it is advantageous to operate with the spacing between the anode and cathode as small as possible in order to keep resistance losses (and therefore electrolytic sliding voltage) to a minimum. At the same time, it is desirable to operate at an economical current density, for example 2L.
However, when using high current densities and small anode/cathode spacings, the rate of gas evolution (eg, chlorine) during electrolysis is high, which can cause bubbles between the gas and the electrolyte.
この気泡は陽極液のある隔室（陽極室）内の陽極准極空
間を部分的に満し、その結果電解液を電解槽から，駆出
せしめかつ少くとも部分的にその後の電解を妨げる。こ
の問題は、例えば英国特許第１１２３３２１号明細書に
記載されるように、気泡を電解槽の外部で破壊してガス
と電解液を分離し、この電解液を陽極室に循環させるこ
とによつて軽減された。更にこの問題は、有孔金属又は
エキスパンデツドメタル製陽極の使用により軽減された
。しかしながら、現存の商業的電解槽を用いては７ｍ７
１ｔより小さい陽極／陰極間隔で操業することは不可能
であり、これは電解槽の効率の点から著しく不利である
。前述の方法により隔膜槽は高い電流密度で比較的小さ
い陽極／陰極間隔で操業できるようになつたが、高、・
電流効率は比較的低い電解槽変換率においてのみ達成さ
れるにすぎない。例えば、塩化ナトリウム水溶液を電解
して塩素と水酸化ナトリウム溶液を得る場合には、９５
〜９６％の電流効率は約５０％の塩変換率で達成される
。よジ高い変換率では電流効率は低下され、例えば６０
０１：Ｉの変換率では約９２沸に、７０％の変換率では
約８４％に低下する。今般本発明者は、従来可能であつ
たよりも小さい有効な陽極／蔭極間隔で操業されしかも
なふ・塩素ガスを制御さ昨たかつ定常的様式で除去Ｃき
かつ低電圧及び高電流効率で、特に高い塩変換率で操業
され得る隔藤槽を案出した。This bubble partially fills the anode quasi-electrode space in the compartment containing the anolyte (anode chamber), thus forcing the electrolyte out of the cell and at least partially preventing further electrolysis. This problem can be solved, for example, by destroying the gas bubbles outside the electrolytic cell to separate the gas and electrolyte and circulating this electrolyte into the anode chamber, as described in British Patent No. 1,123,321. reduced. Additionally, this problem has been alleviated by the use of perforated metal or expanded metal anodes. However, using existing commercial electrolyzers, 7m7
It is not possible to operate with an anode/cathode spacing smaller than 1 t, which is a significant disadvantage in terms of the efficiency of the electrolyzer. Although the method described above allows diaphragm cells to operate at high current densities and relatively small anode/cathode spacings,
Current efficiency is only achieved at relatively low cell conversion rates. For example, when electrolyzing a sodium chloride aqueous solution to obtain a chlorine and sodium hydroxide solution, 95
A current efficiency of ˜96% is achieved with a salt conversion rate of about 50%. At very high conversion rates the current efficiency is reduced, e.g.
At a conversion of 01:I it drops to about 92 boiling points, and at a conversion of 70% it drops to about 84%. The inventors have now discovered that chlorine gas can be removed in a controlled and steady manner while operating at a smaller effective anode/negative electrode spacing than previously possible, and with low voltage and high current efficiency. devised a septa tank that can be operated at particularly high salt conversion rates.
したがつて本？明は、陽極、陰極及び両極を分離する隔
膜を設けた電解槽に卦いて、陽極が該陽極の一部を構成
＋る有孔ないし開口（Ａｐｅｒｔｕｒｅｄ）支持部材と
、多数の縦方向に平行に配置されかつ表面の少なくとも
一部分上に電気触媒的に活性な被膜を有する伸長部材と
からなりかつ該伸長部材が陰極に向くように配置されて
お９、該伸長部材は該支持部材上に間隔を置いてと９つ
けられた刃形、棒状又は溝型部材の形でありこれによつ
て多数の平行な縦型溝を形成するものとし、しかも該伸
長部材は該活性表面の実質的部分が該陰極から６ｍｍ１
又下に位置するように電解槽内に固定して配設されてい
ることを特徴とする改良された電解槽を提供するもので
ある。So a book? The present invention relates to an electrolytic cell having an anode, a cathode, and a diaphragm separating the two electrodes, an apertured support member of which the anode forms part of the anode, and a large number of vertically parallel supporting members. an elongate member disposed and having an electrocatalytically active coating on at least a portion of a surface thereof and oriented such that the elongate member faces the cathode, the elongate member being spaced apart on the support member. in the form of a blade-shaped, rod-shaped or grooved member disposed at a distance 9, thereby forming a plurality of parallel longitudinal grooves; 6mm1 from the cathode
The present invention also provides an improved electrolytic cell characterized in that the electrolytic cell is fixedly disposed within the electrolytic cell so as to be located below.
特公昭４０−２５６１０号公報には、隔膜法電解槽にお
いて陽極が板状、網状、中空板状又は中空網状の形状を
とり得ること及びさらに必要に応じてこれに溝、孔等を
加工して設けることもできることが教示されている。Japanese Patent Publication No. 40-25610 states that in a diaphragm electrolytic cell, the anode can take the shape of a plate, a net, a hollow plate, or a hollow net, and that grooves, holes, etc. may be formed in the anode as necessary. It is taught that it is also possible to provide.
しかしながら、これは既知の型の陽極についての開示で
あり、板状陽極に孔、スリツト等を設けて陽極発生ガス
を陽極背後に抜き出すようにし得ることを述べているに
過ぎず、本発明の特徴とする伸長部材によつて構成され
る多数の平行な縦型溝構造を何等示唆するものではない
。また隔膜法電解槽の陽極板の厚みは通常１龍程度のも
のであるから、ここでいう溝がスリツトでない溝を指す
としても、かかる陽極板に加工される溝は必然的にきわ
めて浅いものとならざるを得ず、本発明の特徴とする溝
構造とはその構成及び作用効果とも全く相違するもので
ある。本発明の特徴とする伸長部材は前述したと卦９陽
極の一部を構成する支持部材上に設けられかつ好ましく
は陰極に向・ナて狭い方の端を呈するものである。伸長
部材は間隔を置いて配置された多数の刃形、棒状あるい
はＵ字、逆Ｕ字又は半円筒形の溝形部材であ９得る。刃
形、例えば一枚刃形の伸長部材を用いることが好ましい
か、刃形の伸長部材は相互に間隔をふ一いて離れかつ強
化目的及び／又は該支持部材への接合のために適当な一
つもしくは二つ以上の連結部材により相互に連結される
二枚刃の形であつてもよい。隣接する伸長部材間の間隔
は実質的ｖ（一定である。However, this is a disclosure of a known type of anode, and merely states that holes, slits, etc. can be provided in the plate-shaped anode to allow the anode-generated gas to be extracted behind the anode, which is a feature of the present invention. There is no suggestion of a multi-parallel vertical groove structure constituted by elongated members. Furthermore, since the thickness of the anode plate of a diaphragm electrolyzer is usually about 1 mm, even if the groove here refers to a groove that is not a slit, the groove machined into such an anode plate is necessarily extremely shallow. Unavoidably, the structure and operation and effect thereof are completely different from the groove structure that characterizes the present invention. The elongated member, which is a feature of the present invention, is provided on the support member forming part of the anode as described above, and preferably presents a narrow end toward and away from the cathode. The elongate member may be a number of spaced apart blade-shaped, rod-shaped or U-shaped, inverted U-shaped or semi-cylindrical channel members. Preferably, blade-shaped elongated members are used, for example single-blade-shaped elongated members, or the blade-shaped elongated members are spaced apart from each other and provided with a suitable length for reinforcement purposes and/or for bonding to the support member. It may also be in the form of two blades interconnected by one or more connecting members. The spacing between adjacent elongate members is substantially v (constant).
これは例えば、多数の二枚刃を用いて両刃を所望の刃間
隔に等しい距離たけ離すことにより達成され得る。この
刃間隔は、例えば１．５〜１０７ｎ７！Ｌ１好ましくは
２〜５ｍ７７！とすることができる。有孔ないし開口（
Ａｐｅｒｔｕｒｅｄ）支持部材（以下支持体装置ともい
−２）としては種々の形態のものを使用し得る。具体的
にいえば、この支持体装置は裏受けの支持（Ｂａｃｋｉ
ｎｇ）板例えば陽極液再循環用の通孔を具えた実質的に
中実の金属製の支持シートより成ることができる。別の
態様では、支持体装置は一つの裏受けの支持枠から成る
こともでき、伸長部材に対して連結するための側方の支
持リブの１個又はそれ以上を具えた支持枠から成るのが
好ましい。この支持枠は長方形であり、しかも前記の伸
長部材の全幅とほぼ等しい距離たけ互に離れた２つの向
き合う内方端縁をもつと共に、この支持枠に対して伸長
部材の終端を連結させ得るために伸長部材の長さよりも
やや短かい距離たけ互に離れた２つの向き合う他の内方
端縁をもつものであるのが都合よい。あるいは、前記の
伸長部材は該部材の各終端に連結された１つの側方の支
持棒部材を具え、しかもこの支持棒が電解槽の底板に連
結する役をするものであつてもよい。This may be achieved, for example, by using a number of double blades and spacing the blades a distance equal to the desired blade spacing. This blade spacing is, for example, 1.5 to 107n7! L1 preferably 2-5m77! It can be done. Perforated or open (
Various forms of support members (hereinafter also referred to as support device-2) can be used. Specifically, this support device is used to support the backing.
ng) The plate may consist, for example, of a substantially solid metal support sheet provided with through holes for anolyte recirculation. In another embodiment, the support device may consist of a backing support frame, the support frame comprising one or more lateral support ribs for coupling to the elongated member. is preferred. The support frame is rectangular and has two opposing inner edges separated by a distance approximately equal to the overall width of the elongate member, and to which the terminal end of the elongate member can be connected. Conveniently, it has two opposing inner edges spaced apart from each other by a distance slightly less than the length of the elongated member. Alternatively, the elongated member may include one lateral support rod member connected to each end of the elongate member, which support rod serves to connect to the bottom plate of the electrolytic cell.
また伸長部材は、第１の側方支持棒から遠い方に位置す
る該伸長部材の終端に連結した別の、すなわち第２の側
方支持棒を具えることもできる。な｝別の実施態様では
、支持体装置は多数の通孔をもつ金属の支持（Ｂａｃｋ
ｉｎｇ）シートから成り、例えば織成した金網、穿孔し
た金寓又はエキスパンデツドメタルから成ることができ
る。The elongate member may also include a further or second lateral support bar connected to a distal end of the elongate member distal to the first lateral support bar. In another embodiment, the support device comprises a multi-perforated metal support.
ing) sheet, which can for example consist of woven wire mesh, perforated wire mesh or expanded metal.
上記いずれの場合にも、かかる有孔ないし開口支持部材
を間隔を置いて配置された多数の刃形、棒状又は溝型部
材と合体した陽極構造体は開放構造、すなわち刃形、棒
状又は溝型部材間に多数の通孔を有し、電解槽中での使
用に際し陽極液の改善された循環を達成し得るものであ
る。In any of the above cases, the anode structure in which such perforated or open support members are combined with a number of spaced apart blade-shaped, rod-shaped or groove-shaped members is an open structure, i.e. blade-shaped, rod-shaped or groove shaped. It has a large number of holes between the parts to achieve improved circulation of the anolyte when used in an electrolytic cell.
伸長部材と支持体装置とは、これらの間に挿設された絶
縁ガスケツトに密に接触した状態で一緒に結着して保持
され得る。The elongate member and support arrangement may be held together in intimate contact with an insulating gasket interposed therebetween.
若しくは伸長部材は熔接により支持体装置に取付けるこ
ともでき、あるいはその構造体の全体を一体として打型
できる。例えば、前述の如き二枚刃を具えた（ＤＯｕｂ
ｌｅｂｌａｄｅｄ）形の伸長部材はそれの架橋連結部に
より支持体装置例えば金属シート、金属枠及びこれの側
方リブ（存在するとして）に対してまた伸長部材の１終
端又は両終端に配置された側方の支持棒に対して熔接さ
れることもできる。伸長部材を、支持枠よりなる支持体
装置、槽底へ連結用の側方の支持棒、又は多数の通孔の
ある支持シートと組合わせると、陽極に実質的に開放し
た構造を与えることになり、すなわち正面から裏面に通
する開放した多数の通路が形成され、しかもこれらの通
路は相隣る伸長部材同志の間の空間によつて定められて
いるものである。Alternatively, the elongated member can be attached to the support device by welding, or the entire structure can be cast as one piece. For example, a device with two blades as mentioned above (DOub
The elongate member of the form (legbladed) is connected by its bridging connections to a support device such as a metal sheet, a metal frame and its lateral ribs (if any) and also to the side located at one or both ends of the elongate member. It can also be welded to one support rod. When the elongated member is combined with a support device consisting of a support frame, lateral support rods for connection to the bottom of the tank, or a support sheet with a number of through holes, it is possible to give the anode a substantially open structure. That is, a number of open passages are formed from the front side to the back side, and these passages are defined by the spaces between adjacent elongated members.
この陽極を隔膜式電解槽で使用すると、陽極（隔膜に対
して極めて近接して存在する）の活性表面と、この陽極
の後方の空間との間に多数の通路が形成されることにな
り、これによつて、陽極液が陽極を通過し得るようにな
る。前記の伸長部材と支持体装置とは被膜形成性金属よ
り成るのが好ましい。When this anode is used in a diaphragm electrolyzer, a number of channels are formed between the active surface of the anode (located in close proximity to the diaphragm) and the space behind this anode. This allows the anolyte to pass through the anode. Preferably, the elongated member and support arrangement are comprised of film-forming metal.
本明細書では、［被膜形成性（ＦＨｍ−ＦＯｒｒｒｌｉ
ｎｇ）金属」とは、チタン金属、ジルコニウム金属、ニ
オブ金属、タンタル金属又はタングステン金鴎、あるい
はこれら金，属の一つを主成分とし且つ前記の純金寓の
陽極分極化性質にほぼ同等な陽極分極化性質をもつ合金
を意味する。チタン単独か又はチタンを主成分とする合
金であつて且つチタン自体のそれとほぼ同等な分極化性
質をもつチタン基合金を用いるのが好ましい。このよう
な合金の例は１４％以下のジルコニウムを含むチタン−
ジルコニウム合金、５％以下の白金族金属例えば白金、
ロジウム、イ、リジウムを含むチタン合金、さらに１０
％以下の合金化成分を含むチタンとニオブ又はタンタル
との合金である。前記の電気触媒的（ＥｌｅｃｔｒＯｃ
ａｔａｌｙｔｉｃａｌｌｙ）に活性な被覆とは、電気化
学的な侵蝕反応に対して耐久性であるが電解液と陽極と
の間で電子を移動させるのには活性である導電性の被覆
である。電気触媒的に活性な材料は１つ又はそれ以上の
白金族金属、すなわち白金、ロジウム、イリジウム、ル
テニウム、オスミウム及びパラジウム、ある・・は該金
属の合金、及び（又は）これらの金寓の酸化物、若しく
は電解槽内での電気化学反応による溶解作用に耐え且つ
陽極として作用するような他の金寓又は化合物、例えば
レニウム、三酸化レニウム、マグネタイト、窒化チタン
並びに白金族金属のホウ化物、リン化物及びケイ化物よ
り成るのが適当である。有効な（０ｐｅｒａｔｉｖｅ）
電極材料よりなる電気触媒的活性な被覆は、当該技術で
公知のように電子不伝導性の酸化物、特にチタンの如き
被膜形成性金寓の酸化物及び（又は）錫のような他の金
属の酸化物をも含有することができ、このような電子不
伝導性の酸化物は、前記の有効な電極材料を前記の被膜
形成性金属製の支持体構造体に対してより確実に結合係
留させるために、また有効な電極材料が作動中の電解槽
中で溶解するのに耐える該材料の耐久性を増大させるた
めに配合されるものである。好適の被覆は白金、白金−
イリジウム合金又は白金族金属酸化物、特に酸化ルテニ
ウム、殊に白金族金属酸化物と被膜形成性金属酸化物と
の混合物例えば酸化ルテニウムと二酸化チタンとの混合
物を含むものである。[Film-forming property (FHm-FOrrrli
ng) "Metal" refers to titanium metal, zirconium metal, niobium metal, tantalum metal, or tungsten metal, or an anode whose main component is one of these metals or metals and whose anodic polarization properties are almost equivalent to the anodic polarization properties of the above-mentioned pure metal. Refers to an alloy with polarizable properties. It is preferable to use titanium alone or a titanium-based alloy that has titanium as its main component and has polarization properties almost equal to that of titanium itself. An example of such an alloy is titanium containing up to 14% zirconium.
Zirconium alloys, up to 5% of platinum group metals, e.g. platinum,
Rhodium, titanium alloy containing rhodium, and 10
% or less of titanium and niobium or tantalum. The electrocatalytic (ElectrOc)
An catalytically active coating is an electrically conductive coating that is resistant to electrochemical erosion reactions but active in transferring electrons between the electrolyte and the anode. Electrocatalytically active materials include one or more platinum group metals, namely platinum, rhodium, iridium, ruthenium, osmium and palladium, alloys of said metals, and/or oxidation of these metals. or other metals or compounds which can withstand the dissolution action of electrochemical reactions in the electrolytic cell and act as anodes, such as rhenium, rhenium trioxide, magnetite, titanium nitride and borides of platinum group metals, phosphorus. Suitably they consist of oxides and silicides. valid (0 perative)
Electrocatalytically active coatings of electrode materials can be made of electronically non-conducting oxides, especially oxides of film-forming metals such as titanium and/or other metals such as tin, as is known in the art. oxides, such electronically non-conducting oxides may also contain oxides, which provide a more secure bonding anchorage of the active electrode material to the film-forming metal support structure. The active electrode material is formulated to increase the durability of the material to withstand dissolution in an operating electrolytic cell. The preferred coating is platinum, platinum-
Iridium alloys or platinum group metal oxides, especially ruthenium oxides, especially mixtures of platinum group metal oxides and film-forming metal oxides, such as mixtures of ruthenium oxide and titanium dioxide.
白金金属の被覆は例えば英国特許第１２３７０７７号に
記載されるように被膜形成性金寓の上に例えば電着法に
よつで形成できる。白金族金寓及びこれらの導電性化合
物特に酸化物は例えば英国特許第３１１４７４４２号、
第１１９５８７１号、第１２０６８６３号及び第１２４
４６５０号に記載される熱分解法によつて容易に製造で
きる。陰極は有孔の金寓シート又は管の形状であるのが
適当である。A coating of platinum metal can be formed on the film-forming metal, for example by electrodeposition, as described in GB 1237077, for example. Platinum group metals and their conductive compounds, especially oxides, are described, for example, in British Patent No. 31147442;
No. 1195871, No. 1206863 and No. 124
It can be easily produced by the pyrolysis method described in No. 4650. The cathode is suitably in the form of a perforated metal sheet or tube.
しかしながら、陰極はこれも支持体装置に設置した多数
の平行な伸長部材より成ることもでき、例えば支持体装
置上に設置した多数の刃状片、棒又は溝（Ｃｈａｎｎｅ
ｌ）部材よりなることができる。特に好ましい陰極は支
持体装置例えば１個の支持枠に設置しだ二枚刃（前述し
た型式の）の多数より成るものである。これらの伸長部
材と支持体装置は軟鋼製であるのが好ましい。支持枠に
取付けた多数の伸長部材よジ成る陰極を用いると、電解
槽内で現場で充填剤を電解的に除去すること（本出願人
の英国特許出願第３４１６８／７３号に記載の如く）に
よつて多孔質の合成樹脂隔膜（例えばポリテトラフルオ
ロエチレン）を作成する場合に充填剤の抽出速度を増大
させる利点がある。However, the cathode can also consist of a number of parallel elongated members, also placed on a support arrangement, for example a number of blades, bars or channels placed on the support arrangement.
l) It can consist of a member. A particularly preferred cathode is one consisting of a plurality of double blades (of the type described above) mounted on a support arrangement, for example a single support frame. Preferably, these elongate members and support arrangements are made of mild steel. The use of a cathode consisting of a number of elongate members mounted on a support frame allows for electrolytic removal of the filler in situ within an electrolytic cell (as described in our UK Patent Application No. 34168/73). This has the advantage of increasing the extraction rate of the filler when making porous synthetic resin membranes (eg polytetrafluoroethylene).
本発明の隔膜槽は低い摺電圧を与えるように陽極一陰極
間隙を６ｍｍ以下として作動できる。The diaphragm cell of the present invention can be operated with an anode-cathode gap of 6 mm or less so as to provide a low sliding voltage.
塩化ナトリウム水溶液を電解する場合、例えば陽極陰極
間の実効間隙を約１，５〜３ｍ７７！に維持できるが、
これに比べて、平担なシート状の陽極を用いる場合に前
記の極間間隙が約７ｍｍである。本発明の電解槽では、
摺電圧は８０〜８５℃で２ＫＡ／ＴＩの電流密度では２
．６〜２。When electrolyzing a sodium chloride aqueous solution, for example, the effective gap between the anode and cathode is approximately 1.5 to 3 m77! can be maintained at
In comparison, when a flat sheet-like anode is used, the gap between the electrodes is about 7 mm. In the electrolytic cell of the present invention,
The sliding voltage is 2 at a current density of 2KA/TI at 80-85℃.
．． 6-2.
８ボルトの範囲である（これに比べて、平担なシート状
の陽極とポリテトラフルオロエチレン隔膜とを用いる場
合に通常は３．０〜３．２ボルトＣある）。8 volts (compared to typically 3.0-3.2 volts C when using a flat sheet anode and a polytetrafluoroethylene membrane).
陽極は実質的に直立して設けるのが好ましいけれども、
直立位置から僅かに傾斜させても電流効率に悪影響しな
い。本発明の隔膜槽は、特に薄膜形成性金属の多数の刃
より成る陽極を用いる場合は、隔膜の寿命を延ばす別の
利点がある。Although it is preferred that the anode be provided substantially upright,
Slight tilting from an upright position will not adversely affect current efficiency. The diaphragm vessel of the present invention has the additional advantage of extending the life of the diaphragm, especially when using a multi-blade anode of film-forming metal.
この利点は、ポリテトラフルオロエチレン又は弗化ポリ
ビニリテンの如き有機重合体を基材とした多孔質の合成
樹脂隔膜を用いる時に特に著るしい。このような隔膜は
、塩化ナトリウム水溶液を電解するときには隔膜の細孔
中に固体（例えば水酸化カルシウム及び水酸化マグネシ
ウム）の沈澱するのに原因して比較的短期間で例えば１
０〜２０日で相当に閉塞するのが普通である。このよう
な沈澱は陰極液のアルカリ性が高いこと並びに電解前に
塩化ナトリウム水溶液を精製した後でも残留するカルシ
ウムイオン及びマグネシウムイオンが存在することによ
り惹起される。本発明でチタンの刃よりなる陽極を用い
る時には、前記の多孔質の合成樹脂隔膜は２４日使用後
でも透過性低下の兆候を示さない。This advantage is particularly significant when using porous synthetic resin membranes based on organic polymers such as polytetrafluoroethylene or polyvinyritene fluoride. Such a diaphragm has the advantage that when electrolyzing aqueous sodium chloride solutions, for example 1
Significant occlusion usually occurs within 0 to 20 days. Such precipitation is caused by the high alkalinity of the catholyte and the presence of residual calcium and magnesium ions even after purifying the aqueous sodium chloride solution prior to electrolysis. When using a titanium blade anode in the present invention, the porous synthetic resin diaphragm does not show any signs of permeability reduction even after 24 days of use.
チタンシート上に設けたチタンの二枚刃をもつ陽極を用
いる過程に訃いて認められたところであるが、塩化ナト
リウムを電解する場合の陽極液のＰＨは、平担なシート
状の陽極を用いた場合に通常得られるＰＨよりも低く、
後者の場合に例えば３．８〜４．５であるのに比べて本
発明の場合には３．２〜３。It has been recognized that the pH of the anolyte when electrolyzing sodium chloride is lower than the pH of the anolyte when using a flat sheet-shaped anode, which is a result of the process using a titanium two-blade anode mounted on a titanium sheet. lower than the pH normally obtained when
For example, it is 3.8-4.5 in the latter case, while it is 3.2-3 in the case of the present invention.
５の範囲である。The range is 5.
このように得られたＰＨの低下は隔膜の寿命向上の点で
恐らく大きな要因をなすものである。本発明の隔膜槽の
別の利点は、苛性ソーダ濃度を上けた時でも、陽極液の
塩素酸塩濃度が従来慣用の平らな板形の陽極を用いた時
に得られた対応の塩素酸塩濃度に比べて減少しているこ
とである。The decrease in pH thus obtained is probably a major factor in improving the life of the diaphragm. Another advantage of the diaphragm tank of the present invention is that even when the caustic soda concentration is increased, the chlorate concentration in the anolyte remains similar to the corresponding chlorate concentration obtained using a conventional flat plate anode. This is a decrease in comparison.
例えば本発明の電解槽は夫々に苛性ソーダ濃度が１２０
〜２１０ｇＮａ０Ｈ／ｌである時に０．０３〜０．５０
ｇｆ）ＣＩＯ３／ｌの塩素酸塩濃度を与えるように作動
できる。比較として、従来慣用の平らな板状の陽極を用
いた場合の対応の塩素酸塩濃度範囲は、苛性ソーダ濃度
範囲が１２０〜２００ｇのＮａＯＨ／ｌである時に０．
５０〜１０．０ｇｆ）ＣｊＯ３／ｌである。本発明は直
立型隔膜式電解槽に応用でき、特にアルカリ金属塩化物
の水溶液、殊に塩化ナトリウム溶液の電解による塩素の
製造用の隔膜槽に応用できる。For example, the electrolytic cells of the present invention each have a caustic soda concentration of 120
0.03-0.50 when ~210gNa0H/l
gf) Can be operated to provide a chlorate concentration of CIO3/l. By way of comparison, the corresponding chlorate concentration range using a conventional flat plate anode is 0.05% when the caustic soda concentration range is 120-200 g NaOH/l.
50-10.0 gf) CjO3/l. The invention is applicable to upright diaphragm electrolytic cells, in particular to diaphragm cells for the production of chlorine by electrolysis of aqueous solutions of alkali metal chlorides, especially sodium chloride solutions.
つぎに第１図〜第１３図を参照しながら、本発明の電解
槽を例を挙げて具体的に説明する。Next, with reference to FIGS. 1 to 13, the electrolytic cell of the present invention will be specifically described by way of example.
第１図に｝いて、陽極は被膜形成性金属、例えばチタン
の板から形成される支持板１と、支持板１（Ｔｃ点溶接
された、被膜形成性金属、例えばチタンから形成された
多数の二枚刃２とから構成される。刃２は電気触媒的に
活性な物質、例えば酸化ルテニウム／二酸化チタン被膜
により被覆される。陽極には更に（後記するごとき）陽
極液を内部循環させるためのスロツト３，４が設けられ
てふーリまた、陽極を電流導入装置に接続するための、
孔６を有するラグ５も設けられている。第２図にむいて
、二枚刃（第１図の多数の二重刃の一個を構成する）は
、一対のあるいは単一の刃７、二枚刃を支持板１に点溶
接するための連結部材８｝よび連結を強化するための連
結部材９とから構成される。In FIG. 1, the anode comprises a support plate 1 made of a plate of a film-forming metal, e.g. titanium, and a number of support plates (Tc spot welded) made of a film-forming metal, e.g. titanium. The blade 2 is coated with an electrocatalytically active substance, such as a ruthenium oxide/titanium dioxide coating. Slots 3 and 4 are provided for connecting the anode to the current introducing device.
A lug 5 with holes 6 is also provided. Referring to FIG. 2, the double blade (constituting one of the many double blades in FIG. A connecting member 8} and a connecting member 9 for strengthening the connection.
第３図に｝いて、水素取出用の出口１１と水酸化ナトリ
ウム取出用の出口１２とを有する好ましくはポリ塩化ビ
ニリデンまたはポリプロピレン製の陰極室１０は、（好
ましくは軟鋼製の）支持板１３と陰極１４（好ましくは
軟鋼製織成鋼）との間に隣接して設置される。In FIG. 3, a cathode chamber 10, preferably made of polyvinylidene chloride or polypropylene, having an outlet 11 for hydrogen extraction and an outlet 12 for sodium hydroxide extraction, is connected to a support plate 13 (preferably made of mild steel). It is placed adjacent to and between the cathode 14 (preferably made of mild woven steel).
陰極１４には、陰極を電流導入装置（図示せず）に連続
するための、孔１６を有するラグ１５が設けられている
。陰極１４は隔膜１７、例えばポリテトラフルオロエチ
レン隔膜を有して｝り、この隔膜は（好ましくは塩化ビ
ニリデン製の）スペーサープレート１８によジ陽極１か
ら分離されている。スペーサープレート１８により陽極
１極の間隔が定められる。塩素（実際には塩素の泡沫と
陽極液）の出口２０、陽極液用排出口２１｝よひ再循環
陽極液（後記参照）用入口２２とを有する、好ましくは
ポリ塩化ビニリデンまたはポリプロピレン製の陽極室１
９は、陽極１の後部と（好ましくはチタン製の）支持板
２３の間に隣接して設置される。第４図にあ・いて、前
記隔膜槽は陰極室１０、陽極室１９｝よび陽極／陰極間
隙２４で表わされている。The cathode 14 is provided with a lug 15 having a hole 16 for connecting the cathode to a current introducing device (not shown). The cathode 14 has a diaphragm 17, for example a polytetrafluoroethylene diaphragm, which is separated from the dianode 1 by a spacer plate 18 (preferably made of vinylidene chloride). The spacer plate 18 defines the distance between the anodes. An anode, preferably made of polyvinylidene chloride or polypropylene, with an outlet 20 for chlorine (actually chlorine foam and anolyte), an outlet 21 for the anolyte, and an inlet 22 for recirculated anolyte (see below). Room 1
9 is placed adjacent between the rear part of the anode 1 and a support plate 23 (preferably made of titanium). In FIG. 4, the diaphragm vessel is represented by a cathode chamber 10, an anode chamber 19} and an anode/cathode gap 24.
陽極室１９は出口２０により液体／ガス分離器２５に連
結しておりこの分離器に卦いて塩素泡沫と陽極液がこれ
らの構成成分に分離される。分離器２５には、塩素の出
口２６、新しいかん水供給口２７訃よび陽極室１９と連
絡してふ−９分離された陽極液を再循環させるための出
口２２が設けられている。電解槽が作動しているときに
は、陽極液は１湯極／陰極間隙２４を上方に流動し、ス
ロツト３を通過しそして２部分に分割される（第４図中
、矢印で示してある）：その一方は直接陽極室１９に流
入しつい−０スロツト４を経て内部方向に流動する（内
部循環），他方は外部方向に流動して分離器２５に流入
しついＣ陽極室に還流する。第５図に卦いて、陽極は横
向の支持リブ２９（点線で示す）と多数の二枚刃３０（
第２図に示した形式のもの）とを有する長方形の金属製
支持枠２８から構成される。The anode chamber 19 is connected by an outlet 20 to a liquid/gas separator 25 in which the chlorine foam and the anolyte are separated into their constituent components. The separator 25 is provided with an outlet 26 for chlorine, a fresh brine supply 27 and an outlet 22 for communicating with the anode chamber 19 and for recirculating the separated anolyte. When the cell is in operation, the anolyte flows upwardly through the hot water electrode/cathode gap 24, passes through the slot 3 and is split into two parts (indicated by arrows in Figure 4): One of them flows directly into the anode chamber 19 and flows inward through the -0 slot 4 (internal circulation), while the other flows outward, flows into the separator 25 and returns to the C anode chamber. In Figure 5, the anode has horizontal support ribs 29 (shown in dotted lines) and a number of double blades 30 (
It consists of a rectangular metal support frame 28 having a structure (of the type shown in FIG. 2).
支持枠２８、リブ２９ち−よび刃３０は被膜形成性金属
、例えばチタンから形成されて卦９、刃３０は支持枠２
８とリブ２９に連結部材により点溶接される。刃３０は
電気触媒的に活性な物質、例えば酸化ルテニウム／二酸
化チタニウム被膜により被覆される。陽極には孔３２を
有する、電流導入装置に陽極を接続するためのラグ３１
が設けられている。第６図に示す装置は陽極１の代りに
第５図に示すごとき陽極Ｖが使用される以外は第３図の
装置と同一である。The support frame 28, the ribs 29, and the blade 30 are made of a film-forming metal, such as titanium.
8 and the rib 29 by a connecting member. The blade 30 is coated with an electrocatalytically active material, such as a ruthenium oxide/titanium dioxide coating. a lug 31 for connecting the anode to a current introducing device, the anode having a hole 32;
is provided. The apparatus shown in FIG. 6 is identical to the apparatus of FIG. 3, except that instead of anode 1, an anode V as shown in FIG. 5 is used.
第７図には、電解槽が作動しているときには、陽極液が
（矢印で示されるごとく）陽極／陰極間隙２４を横切つ
て流動して陽極の刃３０を通過することが示されている
。FIG. 7 shows that when the cell is in operation, the anolyte flows across the anode/cathode gap 24 (as indicated by the arrow) and past the anode blade 30. .
第８図に｝いては、陰極１４は横向きの支持リブ２９′
と多数の２枚刃３０１とを有する長方形の金属支持枠２
８１から構成される。In FIG. 8, the cathode 14 is supported by a horizontal support rib 29'
and a large number of two-blade blades 301.
Consists of 81.
支持枠２８′、リブ２９′お一よび刃３０′は軟鋼によ
り形成され、刃３０′は支持枠２８／とリブ２９′に連
結部材により点溶接される。陰極には孔１４を有する、
陰極を電流導入装置（図示せず）に接続するためのラグ
１５が設けられている。陽極は第５図に示されるものと
同一である。第９図には、電解槽が作動しているときに
は、（矢印で示されるごとく）陽極液は陽極ｒ極間隙２
４を横切つて流動し、陽極の刃３０と陰極の刃３０′を
通過することが示されている。The support frame 28', the ribs 29', and the blade 30' are made of mild steel, and the blade 30' is spot-welded to the support frame 28/and the rib 29' by a connecting member. The cathode has a hole 14,
A lug 15 is provided for connecting the cathode to a current introduction device (not shown). The anode is the same as shown in FIG. FIG. 9 shows that when the electrolytic cell is in operation, the anolyte (as indicated by the arrow) flows into the anode r electrode gap 2.
4 and is shown flowing past the anode blade 30 and the cathode blade 30'.
第１０図に卦いて、隔膜槽は軟鋼製の板状陰極を二分し
た部分体の２個３４，３５｝よび軟鋼製板状中央陰極３
６とを有する軟鋼製陰極箱３３と、共通のチタン製支持
板３９上に互いに背中合せに取ジ付けられた２対のチタ
ン製二枚刃３８から構成される２個の陽極からなる陽極
箱３７とを包含する。As shown in Fig. 10, the diaphragm tank consists of two parts 34, 35, which are obtained by dividing a mild steel plate cathode into two, and a mild steel plate central cathode 3.
6, and an anode box 37 consisting of two anodes consisting of two pairs of titanium double blades 38 mounted back to back on a common titanium support plate 39. and includes.
アスベスト製隔膜４０（第１１図に示す）は対応する陰
極板と陽極の間に適合させて設け、二枚刃３８に近接さ
せる。陽極箱３７と陰極箱３３はフランジ４１，４２に
よジ連結させそしてゴム製ガスケツトを上記陽極箱と陰
極箱の間に挿入する。陰極箱３３には水素排出口４４が
設けられている。頂部カバー４５には塩素排出管４６と
塩化ナトリウム導入管５１が設けられている。隔膜槽に
は更にカセイソーダ排出口４８を有する底部部材４ｒが
設けられている。ゴム製ガスケツト４９，５０を、それ
ぞれ頂部カバー４５と陽極／陰極単位装置の間と、底部
部材４７と陽極／陰極単位装置との間に介在させる。陽
極箱３７と陰極箱３３は、組立てられたときに中央の陽
極液再循環通路が形成され、陽極／陰極の間隙が６ｍｍ
になるように設計される。第１１図には、一対たけの溝
付陽極３８が示されており、この図から電解槽が作動し
ているときには陽極液は矢印で示されるごとく流動する
ことが判る。An asbestos diaphragm 40 (shown in FIG. 11) is fitted between a corresponding cathode plate and anode and is proximate to the biblade 38. The anode box 37 and the cathode box 33 are jointed by flanges 41 and 42, and a rubber gasket is inserted between the anode box and the cathode box. A hydrogen outlet 44 is provided in the cathode box 33 . The top cover 45 is provided with a chlorine discharge pipe 46 and a sodium chloride introduction pipe 51. The diaphragm tank is further provided with a bottom member 4r having a caustic soda outlet 48. Rubber gaskets 49 and 50 are interposed between the top cover 45 and the anode/cathode unit, and between the bottom member 47 and the anode/cathode unit, respectively. The anode box 37 and cathode box 33 form a central anolyte recirculation passage when assembled, with an anode/cathode gap of 6 mm.
is designed to be. A pair of grooved anodes 38 are shown in FIG. 11, and it can be seen from this figure that when the electrolytic cell is in operation, the anolyte flows as indicated by the arrows.
第１２図において、隔膜槽は底部が連結板５４で連結さ
れている多数の陽極の対、５２，５３；５２′， ５３
′からなる陽極組立体を包含する。In FIG. 12, the diaphragm tank has a number of pairs of anodes 52, 53; 52', 53 connected at the bottom by a connecting plate 54.
' includes an anode assembly consisting of.
各陽極は、チタン製支持板５６に取付けられた多数の二
枚刃５５と同様にチタン製の連結板５４とから構成され
る。陽極の対の各々は、連結板５４をＬ字型チタン製棒
５８に溶接することにより隔膜槽のチタン製基板５７に
より支持されかつ電気的に連結され、Ｌ字型チタン製棒
５８は、底部端部が基板５７に溶接されるチタン製棒５
９に溶接される。陽極は第１２図に示されるごとく隣接
する陽極、例えば５３，５２′７＞Ｓ向い合うように配
置される。隔膜を設けられた軟鋼製陰極（図示せず）は
、対峙している陽極対の間に挿入される。第１３図にお
いて、隔膜槽はチタン製棒６１，６２により強固に支持
されている多数の並行しているチタン製の単一の刃６０
からなる陽極組立体を包含する。Each anode is composed of a number of double blades 55 attached to a support plate 56 made of titanium and a connecting plate 54 made of titanium as well. Each of the anode pairs is supported and electrically connected by a titanium substrate 57 of the diaphragm vessel by welding a connecting plate 54 to an L-shaped titanium rod 58, which is connected to the bottom of the titanium rod 58. Titanium rod 5 whose end is welded to the substrate 57
Welded to 9. The anodes are arranged to face adjacent anodes, eg 53, 52'7>S, as shown in FIG. A diaphragm-equipped mild steel cathode (not shown) is inserted between the opposing anode pair. In FIG. 13, the diaphragm vessel has a number of parallel titanium single blades 60 that are rigidly supported by titanium rods 61, 62.
It includes an anode assembly consisting of.
棒６１は隔膜槽のチタン製基板６３に溶接される。隔膜
を設けられた軟鋼製板状陰極は対峙している陽極の間に
挿入される。本発明を更に次の実施例によジ説明するが
本発明はこれに限定されるものではない。The rod 61 is welded to a titanium substrate 63 of the diaphragm tank. A mild steel plate cathode provided with a diaphragm is inserted between opposing anodes. The present invention will be further explained with reference to the following examples, but the present invention is not limited thereto.
実施例 １
用いる陽極（第１図に示した型式のもの）は、二枚刃を
８個点溶接させた１枚のチタン板（１８ゲージ、長さ９
２Ｃ７１１、幅７．６）よりなり、その二枚刃の各々は
１対の平担な矩形のチタン片（１８ゲージ；長さ９０ｃ
ｍ、深さ６ｍ１、４ｍ７Ｋ離して配置）よジなる。Example 1 The anode used (of the type shown in Figure 1) was a titanium plate (18 gauge, length 9) with 8 double blades welded at points.
2C711, width 7.6), each of its two blades consists of a pair of flat rectangular titanium pieces (18 gauge;
m, depth 6m1, spaced 4m7K apart).
前記刃を酸化ルテニウム／二酸化チタンの混合物で被覆
する。こうして作製した陽極を第３図に示した型式の且
つ前記の如き直立型の実験用隔膜式電解槽中に組込む。The blade is coated with a ruthenium oxide/titanium dioxide mixture. The anode thus prepared is assembled into an experimental diaphragm electrolytic cell of the type shown in FIG. 3 and of the upright type described above.
該電解槽は軟鋼の織成した金網製陰極とポリテトラフル
オロエチレン製隔膜とを備えている。陽極と陰極との間
隔は１．５乃至２，０ｍ７７！である。電解槽に塩化ナ
トリウムの飽和ガン水を充填し、２ＫＡ／ｍ”の陰極電
流密度に相当する電流を電解槽に流す。電解槽の作動電
圧は２．６８Ｖであることが見出された。電解は種々異
なる塩の転化率で（供給食塩水の流量を加減することに
より）行い、得られた電流効率は次の如くである；３．
１乃至３．２のＰＨ値（５０％の転化率で）が陽極液室
内に維持され、更に５０％の塩転化率で電解槽を２４日
間作動させた後でも隔膜の透過性が失われていないこと
が明らかに認められた。The electrolytic cell is equipped with a cathode made of a wire mesh woven from mild steel and a diaphragm made of polytetrafluoroethylene. The distance between the anode and cathode is 1.5 to 2.0m77! It is. The electrolytic cell was filled with gun water saturated with sodium chloride, and a current corresponding to a cathode current density of 2 KA/m'' was passed through the electrolytic cell. The operating voltage of the electrolytic cell was found to be 2.68 V. were carried out at different salt conversions (by adjusting the flow rate of the supplied brine), and the current efficiencies obtained were as follows; 3.
A pH value of 1 to 3.2 (at 50% conversion) was maintained in the anolyte chamber, and even after operating the cell for 24 days at 50% salt conversion, there was no loss of membrane permeability. It was clearly acknowledged that there was no.
比較のため、前記で用いた陽極と全体の寸法が同じ平担
なチタン板陽極を用いしかも同じ酸化ルテニウム／二酸
化チタン被覆層を担持する陽極を用いて電解槽を作動さ
せる。用いた通常の陽極／陰極の間隔は７０ｍｍとした
。２ＫＡ／イの電流密度では、この比較の電解槽の作動
電圧は本発明の刃型の陽極を用いた時よジもずつと高く
、即ち本発明の２．６８Ｖの代ジに３．１０Ｖであつた
。For comparison, an electrolytic cell is operated using a flat titanium plate anode having the same overall dimensions as the anode used above and carrying the same ruthenium oxide/titanium dioxide coating layer. The usual anode/cathode spacing used was 70 mm. At a current density of 2 KA/A, the operating voltage of this comparative electrolyzer is much higher when using the blade-shaped anode of the present invention, i.e., 3.10 V compared to 2.68 V of the present invention. It was hot.
塩の転化率が増大すると共に電流効率か降下する度合も
以下に示される如くずつと大きい。；３．９０乃至４．
５０のＰＨ値（５０％の転化率で）が陽極液室で維持さ
れ、１０日間に亘つて隔膜の透過性が除々に失われてい
くことが見られ、その後には隔膜を例えば食塩水で洗浄
することによリ清浄化することが必要となつた。As the salt conversion increases, the current efficiency decreases to a greater extent as shown below. ;3.90 to 4.
A pH value of 50 (at 50% conversion) was maintained in the anolyte chamber and a gradual loss of permeability of the membrane was observed over a period of 10 days, after which the membrane was washed with e.g. saline. It became necessary to reclean by washing.
実施例 ２
用いる陽極は実施例１で用いたのと同じ寸法を有するも
のであるが、この場合には二枚刃はチタン板の代ジに１
個の矩形状のチタン支持枠に点溶接されている（即ち用
いる陽極は第５図に示した型式のものである）。Example 2 The anode used has the same dimensions as used in Example 1, but in this case the two-blade blade is 1.
(i.e., the anode used is of the type shown in FIG. 5).
これは第４図に示した一方向に流れる（Ｄｉｒｅｃｔｅ
ｄ）内部循環を実際に除去するものである。陽極を実施
例１に記載したのと同じ酸化ルテニウム／酸化チタン被
覆層で被覆する。１．５乃至２．０ｍ７！Ｌの陽極／陰
極の間隔（実施例１の如く）を用い、２ＫＡ／ＴＩの電
流密度で、電解槽作動電圧は２．７６Ｖとした。This flows in one direction as shown in Figure 4.
d) It actually eliminates internal circulation. The anode is coated with the same ruthenium oxide/titanium oxide coating layer as described in Example 1. 1.5~2.0m7! Using an anode/cathode spacing of L (as in Example 1) and a current density of 2 KA/TI, the cell operating voltage was 2.76 V.
塩の転化率が増人するにつれて電流効率が降下する度合
は、実施例１「刃型］チタン板陽極を用いた時よジも幾
分大きいが、平担なチタン板陽極を用いた時に見られる
電流効率の降下度ほどには入きくない。得られた結果は
次の如くである；３。The degree to which the current efficiency decreases as the salt conversion rate increases is somewhat larger than in Example 1 when a blade-shaped titanium plate anode is used, but it is seen when a flat titanium plate anode is used. The drop in current efficiency is not as great as the drop in current efficiency.The results obtained are as follows;3.
３乃至３．４のＰＨ値（５０％の塩転化率で）が陽極液
室で維持され、２５日間に亘つて隔膜の透過性が除々に
失われることが見られ、その後には隔膜を例えば食塩水
で洗浄することによ沙清浄化することが必要となつた。A pH value of 3 to 3.4 (at 50% salt conversion) was maintained in the anolyte chamber and a gradual loss of permeability of the membrane was observed over a period of 25 days, after which the membrane was removed e.g. It became necessary to cleanse the area by washing with saline.
実施例 ３
用いる陽極（第５図に示した型式のもの）は二枚刃の２
９個を具えたチタン（１８ゲージ）板の５８枚よジなジ
、二枚刃の各刃は長さ４３ｃｍ、深さ７騙であシ、相継
続する刃同志の間の間隔は４ｍ７！Ｌである。Example 3 The anode used (of the type shown in Figure 5) was a two-blade type.
58 pieces of titanium (18 gauge) plate with 9 pieces, each double-edged blade is 43cm long and 7mm deep, and the distance between successive blades is 4m7! It is L.
前記の二枚刃はチタンフレーム２８及び２つのチタンリ
ブ２９に点溶接されている。前記刃を酸化ルテニウム／
二酸化チタンの混合物で被覆する。こうして作製した陽
極を第６図に示した型式の且つ前記の如き直立型の実験
用隔膜式電解槽中に組込む。Said two blades are spot welded to a titanium frame 28 and two titanium ribs 29. The blade is made of ruthenium oxide/
Coat with a mixture of titanium dioxide. The anode thus prepared is assembled into an experimental diaphragm electrolytic cell of the type shown in FIG. 6 and of the upright type described above.
該電解槽は軟鋼の織成した金網製陰極とポリテトラフル
オロエチレン製隔膜とを備えている。陽極／陰極の間隔
は２．５乃至３．０ｍ７ＩＬである。得られた結果は次
の如くである。′
電解槽に塩化ナトリウム飽和水溶液を充填し、２ＫＡ／
ｍｌの陰極電流密度に当量の電流を電解槽に流す。The electrolytic cell is equipped with a cathode made of a wire mesh woven from mild steel and a diaphragm made of polytetrafluoroethylene. The anode/cathode spacing is 2.5-3.0 m7IL. The results obtained are as follows. ' Fill the electrolytic cell with a saturated aqueous solution of sodium chloride and
A current equivalent to the cathode current density in ml is passed through the electrolytic cell.
電解槽作動電圧は２．７Ｖであることが見出された。電
解槽を５０（ｆ）の食塩転化率で作動させた時には、３
．４のＰＨ値が陽極液室で維持され、更に２４日間の作
動後でも隔膜の透過性が失われることはないことが明ら
かである。The electrolyzer operating voltage was found to be 2.7V. When the electrolyzer is operated at a salt conversion rate of 50(f), 3
．． It is clear that a pH value of 4 is maintained in the anolyte chamber and that even after 24 days of operation there is no loss of permeability of the membrane.
実施例 ４
用いる陽極は２９個の二枚刃から構成されたチタン（１
８ゲージ）板の５８枚よりなり、二枚刃の各々の刃は長
さ４３ｃ７ｒＬ１深さ７ｊｕであり、相継続する刃同志
の間の間隔は４ｍ７！Ｌである。Example 4 The anode used was made of titanium (1
It consists of 58 pieces of 8 gauge) plates, each of the two blades is 43cm7rL1 in length and 7ju in depth, and the spacing between successive blades is 4m7! It is L.
前記の二枚刃はチタン支持枠１及び２つのチタン、リブ
２に点溶接されてある。前記刃を酸化ルテニウム／二酸
化チタンの混合物で被覆させる。用いる陰極は２９個の
二枚刃を具えた軟鋼板の５８枚よりなり、各々の刃は長
さ４３ＣＴｒＬ、深さ７ｍｍであり、相継続する刃同志
の間の間隔は４韮である。The two blades are spot welded to a titanium support frame 1 and two titanium ribs 2. The blade is coated with a ruthenium oxide/titanium dioxide mixture. The cathode used consisted of 58 mild steel plates with 29 double blades, each blade having a length of 43 CTrL and a depth of 7 mm, and the spacing between successive blades was 4 squares.
前記の二枚刃は軟鋼の支持枠１及び２つの軟鋼リブ２に
点溶接されてある。こうして作製した陽極卦よび陰極を
第６図に示した型式の且つ前記の如き直立型の実験用隔
膜式電解槽中に組込む。Said two blades are spot welded to a mild steel support frame 1 and two mild steel ribs 2. The anode and cathode thus prepared are assembled into an upright experimental diaphragm electrolytic cell of the type shown in FIG. 6 and as previously described.
該電解槽にポリテトラフルオロエチレン製隔膜を設ける
。陽極／陰極の間隔は１．５乃至２．０７７ｔｍである
。電解槽に塩化ナトリウムの飽和水溶液を充填し２幻Ｖ
背の陰極電流密度に相当する電流を電解槽に流す。A polytetrafluoroethylene diaphragm is provided in the electrolytic cell. The anode/cathode spacing is between 1.5 and 2.077 tm. Fill the electrolytic tank with a saturated aqueous solution of sodium chloride and
A current corresponding to the back cathode current density is passed through the electrolytic cell.
電解槽作動電圧は２．６５乃至２．７Ｖであることが見
出された。電解槽を５０％の食塩転化率で作動させた時
には、３．２乃至３．４のＰＨ値が陽極液室で維持され
、更に２４日間の作動後でも隔膜の透過性が失われるこ
とがないことは明らかであ？）。The cell operating voltage was found to be 2.65-2.7V. When the electrolyzer is operated at 50% salt conversion, a pH value of 3.2 to 3.4 is maintained in the anolyte chamber, and the permeability of the diaphragm is not lost even after 24 days of operation. Is that clear? ).
実施例 ５
３０個の二枚刃を１枚の中実チタン板に点溶接すること
により高さ１００ＣＴ！Ｌ、幅３２ｃ１ｎの寸法を有す
る陽極１個を得る。Example 5: 100CT height by spot welding 30 double blades to one solid titanium plate! One anode having dimensions L and width 32c1n is obtained.
このような陽極２個を垂直なチタン製Ｕ一字スペーサー
部品により背中合せに接合して箱形の陽極を得る。但し
その接合は前記箱形の陽極の箱体内で内部の液の循環、
降下、が起Ｄ得るように行われる。この得られた陽極構
造体を実施例１に記載したのと同じ酸化ルテニウム／酸
化チタン被覆層で被覆する。このような陽極構造体の２
つを第１０図に示した型式の直立型の隔膜式電解槽中に
組込む。Two such anodes are joined back to back by a vertical titanium U-shaped spacer part to obtain a box-shaped anode. However, this bonding is achieved by the circulation of internal liquid within the box body of the box-shaped anode,
The descent is carried out in such a way that it can be taken off. The resulting anode structure is coated with the same ruthenium oxide/titanium oxide coating layer as described in Example 1. 2 of such anode structure
One is assembled into an upright diaphragm electrolytic cell of the type shown in FIG.
この電解槽は指状に三分された陰極を収容し、この陰極
の指部分の２つは高さ１００ＣＴＩＬ１幅３２ｃｍの寸
法を有し且つこれらの間に残ｖの指部分が中央陰極とし
て配置される。前記の陰極組立体は厚さ２乃至３ｍ７！
Ｌの沈着させたクリソタイル型の石綿隔膜で前もつて被
覆されているものである。陽極／陰極の間隔は６ｍ７１
Ｌである。電解槽に塩化ナトリウムの飽和水溶液を充填
し、２．５ＫＡ／ｍ”の陰極電流密度に相当する量の電
流を電解槽に流す。This electrolytic cell accommodates a cathode divided into three finger-shaped parts, two of which have dimensions of 100 CTIL 1 width 32 cm, and between these the remaining fingers are arranged as a central cathode. be done. Said cathode assembly has a thickness of 2 to 3 m7!
It was previously coated with a chrysotile-type asbestos membrane deposited by L. Anode/cathode spacing is 6m71
It is L. The electrolytic cell is filled with a saturated aqueous solution of sodium chloride, and a current corresponding to a cathode current density of 2.5 KA/m'' is passed through the electrolytic cell.
電解槽作動電圧（チタン乃至軟鋼）は３．３３Ｖである
と見出された。電流効率の結果は次の如くである；本発
明の実施態様を要約すれば次の通ｖである。The cell operating voltage (titanium to mild steel) was found to be 3.33V. The current efficiency results are as follows; the embodiments of the present invention can be summarized as follows.
（１）伸長部材を陽極の一部を構成する支持部材上に設
けること。（２）伸長部材がその狭い方の端を陰極に向
けて呈すること。(1) Providing the elongated member on a support member that constitutes a part of the anode. (2) The elongate member presents its narrow end toward the cathode.
（３）伸長部材が支持部材上に設けられた刃形、棒状又
は溝形のものであること。(3) The elongated member has a blade shape, a rod shape, or a groove shape provided on the support member.
（４）伸長部材が相互に間隔をおいて離れかつ強化目的
及び／又は該支持部材への接合のために極当な一つもし
くは二つ以上の連結部材により相互に連結される二枚刃
形のものであること。(4) Two-blade type in which the elongated members are spaced apart from each other and connected to each other by one or more connecting members suitable for reinforcement purposes and/or for joining to the supporting member. Be of.
（５）隣接する伸長部材間の距離が１．５〜１０ｍ７！
Ｌであること。（６）隣接する伸長部材間の距離が２〜
５關であること。(5) The distance between adjacent extension members is 1.5 to 10m7!
Being L. (6) The distance between adjacent elongated members is 2 or more
5. Be relevant.
（７）前記の支持部材が支持板からなること。(7) The support member may be a support plate.
（８）前記の支持部材が陽極液を循環させるための孔を
設けた実質的に固体の金属製シートであること。（９）
支持部材が支持枠からなること。(8) The support member is a substantially solid metal sheet provided with holes for circulating the anolyte. (9)
The support member consists of a support frame.
ＵＯ）前記の支持枠に、伸長部材への連結用の一つ又は
二つ以上の横支持リブを設けること。UO) Providing said support frame with one or more lateral support ribs for connection to the elongated member.
００支持部材が、伸長部材を電解槽の基板に連結させる
のに適当でありかつ伸長部材の一端に連結された横支持
棒からなること。00 support member is suitable for connecting the elongate member to the substrate of the electrolytic cell and comprises a lateral support bar connected to one end of the elongate member.
（２支持部材が多孔支持シートからなること。(2) The support member is made of a porous support sheet.
（へ）前記の多孔金属製支持シートが織成絽紗、ドリル
ドプレート又はエキスパンデツドメタルからなること。
（ニ）伸長部材が被膜形成性金属からなること。(f) The porous metal support sheet is made of woven gauze, drilled plate, or expanded metal.
(d) The elongated member is made of a film-forming metal.
（ホ）前記の被膜形成性金属がチタン又はチタン合金で
あること。（ホ）電気触媒的に活性な被膜が白金族金属
の酸化物及び被膜形成性金寓の酸化物からなること。(e) The film-forming metal is titanium or a titanium alloy. (e) The electrocatalytically active coating consists of an oxide of a platinum group metal and an oxide of a film-forming metal.
（７）前記の被膜が酸化ルテニウム及び酸化チタンから
なること。（ト）陰極が有孔金属板又は管からなること
。(7) The coating is made of ruthenium oxide and titanium oxide. (g) The cathode consists of a perforated metal plate or tube.
（株）陰極が支持部材上に設けられた多数の平行な伸長
部材からなること。（至）陰極が支持部材上に設けられ
た多数の刃、棒又は溝形の部材からなること。Co., Ltd. The cathode consists of a number of parallel elongated members provided on a support member. (To) The cathode consists of a number of blades, rods, or groove-shaped members provided on a support member.
（自）陰極が相互に間隔を｝いて離れかつ強化目的及び
／又は該支持部材への接合のために適当な一つもしくは
二つ以上の連結部材により相互に連結される二枚刃の形
の多数の平行な伸長部材からなること。in the form of two blades, the cathodes being spaced apart from each other and connected to each other by one or more connecting members suitable for reinforcing purposes and/or for bonding to the support member. consisting of a number of parallel elongated members.
＠ 陰極が軟鋼製のものであること。@ The cathode must be made of mild steel.
（ハ）隔膜がポリテトラフルオロエチレンからなること
。(c) The diaphragm is made of polytetrafluoroethylene.
９隔膜がアスベストからなること。9. The diaphragm is made of asbestos.
（至）陽極准極間隔を１．５〜３ｍｍとすること。(To) The anode quasi-electrode spacing should be 1.5 to 3 mm.
（至）陽極の伸長部材を電解槽内に実質的に垂直に設け
ること。（支）電解槽をアルカリ金属塩化物水溶液の電
解に用いること。(to) Providing the elongated member of the anode substantially vertically within the electrolytic cell. (Support) Use of an electrolytic cell for electrolysis of aqueous alkali metal chloride solutions.
（４）電解槽を塩化ナトリウム液（食塩水）の電解に用
いること。(4) Use an electrolytic cell for electrolysis of sodium chloride solution (salt water).
第１図は、支持板とこれに取付けられた多数の二枚刃形
伸長部材とからなる陽極の透視図である。
第２図は、第１図または第５図の陽極あるいは第８図の
陰極の構成に使用するのに適当な二枚刃形伸長部材の透
視図である。第３図は、塩化ナトリウム水溶液の電解に
使用される第１図の陽極を設けた本発明による実験室用
垂直型隔膜槽の構成部材を示す分解図である。第４図は
、第３図の隔膜槽に卦ける陽極液の循環系を示す流れ図
である。第５図は、支持枠とこれに取付けられた多数の
二枚刃形伸長部材とからなる陽極の透視図である。第６
図は、塩化ナトリウム水溶液の電解に使用される第５図
の陽極を設けた本発明による実験室用垂直型隔膜槽の構
成部材を示す分解図である。第７図は、第６図の隔膜槽
に卦ける陽極液の循環系を示す流れ図である。第８図は
、塩化ナトリウム水溶液の電解に使用される、第５図の
陽極訃よひ第５図の陽極と同様の形状の陰極を設けた本
発明による実験室用垂直型隔膜槽の構成部材を示す分解
図である。第９図は、第８図の隔膜槽に訃ける陽極液の
循環系を示す流れ図である。第１０図は、塩化ナトリウ
ム水溶液の電解に使用される、支持板に取り付けられた
多数の伸長部材とアスベスト隔膜とからなる両面陽極を
設けた本発明による実験室用垂直型隔膜槽の構成部材を
示す分解図である。第１１図は、第１０図の隔膜槽に卦
ける陽極液の循環系を示す流れ図である。第１２図は、
各陽極が支持板に取付けられた多数の二枚刃形伸長部材
からなりかつ陽極が一対づつ隔膜槽の基板上に設けられ
た棒状部材に連結されている、本発明による垂直型隔膜
槽中の陽極組立体の透視図である。第１３図は、陽極の
各対が、隔膜槽の基板上に設けられた横支持棒にその基
部が連結されている多数の一枚刃形伸長部材によつて形
成されている、本発明による垂直型隔膜槽中の陽極組立
の透視図である。１・・・支持板、２・・・二枚刃、３
，４・・・スロツト、１０・・・陰極室、１４・・・陰
極、１７・・・隔膜、１９・・・陽極室、２５・・・分
離室、２８・・支持枠。FIG. 1 is a perspective view of an anode consisting of a support plate and a number of two-blade elongate members attached thereto. FIG. 2 is a perspective view of a two-blade elongated member suitable for use in the construction of the anode of FIG. 1 or 5 or the cathode of FIG. 8; FIG. 3 is an exploded view showing the components of a vertical diaphragm cell for laboratory use according to the invention, which is provided with the anode of FIG. 1 used for the electrolysis of an aqueous sodium chloride solution. FIG. 4 is a flowchart showing the anolyte circulation system in the diaphragm tank of FIG. FIG. 5 is a perspective view of an anode consisting of a support frame and a number of two-blade elongated members attached thereto. 6th
The figure is an exploded view showing the components of a vertical diaphragm cell for laboratory use according to the invention, which is provided with the anode of FIG. 5, used for the electrolysis of aqueous sodium chloride solutions. FIG. 7 is a flowchart showing the anolyte circulation system in the diaphragm tank of FIG. 6. FIG. 8 shows the components of a vertical diaphragm tank for a laboratory according to the present invention, which is used for electrolysis of an aqueous sodium chloride solution and is equipped with an anode shown in FIG. 5 and a cathode having a similar shape to the anode shown in FIG. 5. FIG. FIG. 9 is a flowchart showing the circulation system of the anolyte flowing into the diaphragm tank of FIG. FIG. 10 shows the components of a vertical diaphragm tank for a laboratory according to the invention, which is used for the electrolysis of an aqueous sodium chloride solution and is equipped with a double-sided anode consisting of a number of elongated members attached to a support plate and an asbestos diaphragm. FIG. FIG. 11 is a flowchart showing the anolyte circulation system in the diaphragm tank of FIG. 10. Figure 12 shows
In a vertical diaphragm cell according to the invention, each anode comprises a number of two-blade elongate members mounted on a support plate, and the anodes are connected in pairs to rod-like members provided on the substrate of the diaphragm cell. FIG. 3 is a perspective view of the anode assembly. FIG. 13 shows the present invention in which each pair of anodes is formed by a multiplicity of single-blade elongate members connected at their bases to lateral support bars provided on the substrate of the diaphragm vessel. FIG. 2 is a perspective view of an anode assembly in a vertical diaphragm tank. 1...Support plate, 2...Two blades, 3
, 4... Slot, 10... Cathode chamber, 14... Cathode, 17... Diaphragm, 19... Anode chamber, 25... Separation chamber, 28... Support frame.
Claims (1)
において、陽極が該陽極の一部を構成する有孔ないし開
口支持部材と、多数の縦方向に平行に配置されかつ表面
の少なくとも一部分上に電気触媒的に活性な被膜を有す
る伸長部材とからなりかつ該伸長部材が陰極に向くよう
に配置されており、該伸長部材は該支持部材上に間隔を
置いてとりつけられた刃形、棒状又は溝型部材の形であ
りこれによつて多数の平行な縦型溝を形成するものとし
、しかも該伸長部材は該活性表面の実質的部分が該陰極
から６ｍｍ以下に位置するように電解槽内に固定して配
設されていることを特徴とする改良された電解槽。1. In an electrolytic cell equipped with a diaphragm separating an anode, a cathode, and both electrodes, the anode is arranged in parallel with a perforated or open support member forming a part of the anode in a plurality of longitudinal directions and on at least a portion of the surface. an elongate member having an electrocatalytically active coating on the support member, and the elongate member is arranged to face the cathode, and the elongate member includes blade-shaped, rod-shaped, and rod-shaped parts mounted at intervals on the support member. or in the form of a channel-shaped member, thereby forming a plurality of parallel longitudinal grooves, and wherein the elongated member is arranged in the electrolytic cell such that a substantial portion of the active surface is located no more than 6 mm from the cathode. An improved electrolytic cell characterized in that the electrolytic cell is fixedly disposed within the electrolytic cell.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4468273A GB1479444A (en) | 1974-07-04 | 1973-09-24 | Electrolytic cells |
| GB4468273 | 1973-09-24 | ||
| GB2968374 | 1974-07-04 | ||
| GB2968374 | 1974-07-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5077274A JPS5077274A (en) | 1975-06-24 |
| JPS599634B2 true JPS599634B2 (en) | 1984-03-03 |
Family
ID=26260027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP49108931A Expired JPS599634B2 (en) | 1973-09-24 | 1974-09-24 | improved electrolyzer |
Country Status (19)
| Country | Link |
|---|---|
| US (1) | US4013525A (en) |
| JP (1) | JPS599634B2 (en) |
| AR (1) | AR202842A1 (en) |
| AT (1) | AT333789B (en) |
| BE (1) | BE820295A (en) |
| CA (1) | CA1034080A (en) |
| CH (1) | CH603818A5 (en) |
| DD (1) | DD115582A5 (en) |
| DE (1) | DE2445579A1 (en) |
| ES (1) | ES430317A1 (en) |
| FI (1) | FI60038C (en) |
| FR (1) | FR2244836B1 (en) |
| IL (1) | IL45747A (en) |
| IN (1) | IN142302B (en) |
| IT (1) | IT1022229B (en) |
| NL (1) | NL7412586A (en) |
| NO (1) | NO139744C (en) |
| SE (1) | SE7411935L (en) |
| TR (1) | TR18082A (en) |
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| GB1581348A (en) * | 1976-08-04 | 1980-12-10 | Ici Ltd | Bipolar unit for electrolytic cell |
| GB1581347A (en) * | 1976-08-04 | 1980-12-10 | Ici Ltd | Resilient anodes |
| GB1581534A (en) * | 1976-09-20 | 1980-12-17 | Ici Ltd | Electrolytic cell |
| JPS5460278A (en) * | 1977-10-21 | 1979-05-15 | Kureha Chem Ind Co Ltd | Diaphragm type electrolytic bath |
| US4132622A (en) * | 1977-11-30 | 1979-01-02 | Hooker Chemicals & Plastics Corp. | Bipolar electrode |
| US4274928A (en) * | 1978-07-27 | 1981-06-23 | Ppg Industries, Inc. | Process for electrolyzing brine in a permionic membrane electrolytic cell |
| US4211627A (en) * | 1978-07-27 | 1980-07-08 | Ppg Industries, Inc. | Permionic membrane electrolytic cell |
| US4165272A (en) * | 1978-07-27 | 1979-08-21 | Ppg Industries, Inc. | Hollow cathode for an electrolytic cell |
| IT1163737B (en) * | 1979-11-29 | 1987-04-08 | Oronzio De Nora Impianti | BIPOLAR ELECTROLIZER INCLUDING MEANS TO GENERATE THE INTERNAL RECIRCULATION OF THE ELECTROLYTE AND ELECTROLYSIS PROCEDURE |
| DE3005795C2 (en) * | 1980-02-15 | 1984-12-06 | Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach | Coated metal anode for the electrolytic extraction of metals |
| DE3170397D1 (en) * | 1980-07-30 | 1985-06-13 | Ici Plc | Electrode for use in electrolytic cell |
| US4370215A (en) * | 1981-01-29 | 1983-01-25 | The Dow Chemical Company | Renewable electrode assembly |
| DE3219704A1 (en) * | 1982-05-26 | 1983-12-01 | Uhde Gmbh, 4600 Dortmund | MEMBRANE ELECTROLYSIS CELL |
| DE3401638A1 (en) * | 1984-01-19 | 1985-07-25 | Hoechst Ag, 6230 Frankfurt | ELECTROLYSIS PROCESS WITH LIQUID ELECTROLYTE AND POROUS ELECTRODES |
| DE3519272C1 (en) * | 1985-05-30 | 1986-12-18 | Heraeus Elektroden GmbH, 6450 Hanau | Electrode structure for electrochemical cells |
| DE3519573A1 (en) * | 1985-05-31 | 1986-12-04 | Conradty GmbH & Co Metallelektroden KG, 8505 Röthenbach | ELECTRODE FOR MEMBRANE ELECTROLYSIS |
| DE3613997A1 (en) * | 1986-04-25 | 1987-10-29 | Sigri Gmbh | ANODE FOR ELECTROLYTIC PROCESSES |
| BR9007455A (en) * | 1989-06-23 | 1992-06-16 | Heraeus Elektrochemie | ELECTROLYSIS CELL FOR ELECTRIC PROCESSES GAS GENERATORS |
| US5531873A (en) * | 1990-06-20 | 1996-07-02 | Savcor-Consulting Oy | Electrode arrangement to be used in the cathodic protection of concrete structures and a fixing element |
| DE4119836A1 (en) * | 1991-06-12 | 1992-12-17 | Arnold Gallien | ELECTROLYSIS CELL FOR GAS DEVELOPING OR GAS-CONSUMING ELECTROLYTIC PROCESSES AND METHOD FOR OPERATING THE ELECTROLYSIS CELL |
| US5322604A (en) * | 1992-11-02 | 1994-06-21 | Olin Corporation | Electrolytic cell and electrodes therefor |
| US5340457A (en) * | 1993-04-29 | 1994-08-23 | Olin Corporation | Electrolytic cell |
| US6497947B1 (en) * | 1999-08-16 | 2002-12-24 | Ford Global Technologies, Inc. | Interior automotive trim member having improved scratch resistance and a method of making the same |
| DE102005003526A1 (en) * | 2005-01-25 | 2006-07-27 | Uhdenora S.P.A. | An electrolytic cell is formed in two half shells the walls of which are pressed from a single sheet of material which has no joints |
| ITMI20050108A1 (en) * | 2005-01-27 | 2006-07-28 | De Nora Elettrodi Spa | ANODE SUITABLE FOR GAS DEVELOPMENT REACTIONS |
| US20060266381A1 (en) * | 2005-05-27 | 2006-11-30 | Doherty James E | Commercial glassware dishwasher and related method |
| US11105011B2 (en) * | 2015-02-02 | 2021-08-31 | Hci Cleaning Products, Llc | Chemical solution production |
| WO2020245650A1 (en) * | 2019-06-07 | 2020-12-10 | Dmitry Medvedev | System and method of nanocarbon materials manufacturing by pulse electric discharge in liquid |
| CN110760894A (en) * | 2019-10-28 | 2020-02-07 | 昆明冶金研究院 | Preparation method of titanium coating anode |
| EP4248503A1 (en) * | 2020-11-23 | 2023-09-27 | Lawrence Livermore National Security, LLC | Corrugated electrodes for electrochemical applications |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4857899A (en) * | 1971-11-09 | 1973-08-14 |
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| US1269566A (en) * | 1917-07-05 | 1918-06-11 | Toronto Power Company Ltd | Electrolytic apparatus. |
| US1548840A (en) * | 1924-07-23 | 1925-08-11 | Nordiske Fabriker De | Electrode for electrolytic decompostion apparatus |
| FR602561A (en) * | 1925-07-04 | 1926-03-22 | Nordiske Fabriker De No Fa Akt | electrode for electrolysers |
| FR1251050A (en) | 1959-03-11 | 1961-01-13 | Hoechst Ag | metal electrodes for electrolysis cells |
| US3507771A (en) * | 1966-09-30 | 1970-04-21 | Hoechst Ag | Metal anode for electrolytic cells |
| ZA703723B (en) | 1969-06-24 | 1972-01-26 | Ppg Industries Inc | Diaphragm cell |
| GB1313298A (en) | 1969-06-27 | 1973-04-11 | Ici Ltd | Anode assembly for electrolytic cells |
| GB1304518A (en) * | 1969-06-27 | 1973-01-24 | ||
| BE755592A (en) | 1969-09-02 | 1971-03-02 | Ici Ltd | ANODIC ASSEMBLY |
| DE2059868B2 (en) * | 1969-12-06 | 1974-07-25 | Nippon Soda Co., Ltd., Tokio | Electrode plate to be arranged vertically for gas-forming electrolysis |
| GB1336225A (en) | 1970-07-09 | 1973-11-07 | Nippon Soda Co | Electrolytic cell |
| US3803016A (en) * | 1972-02-09 | 1974-04-09 | Fmc Corp | Electrolytic cell having adjustable anode sections |
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1974
- 1974-09-19 US US05/507,603 patent/US4013525A/en not_active Expired - Lifetime
- 1974-09-23 IT IT27605/74A patent/IT1022229B/en active
- 1974-09-23 IN IN2115/CAL/74A patent/IN142302B/en unknown
- 1974-09-23 SE SE7411935A patent/SE7411935L/xx unknown
- 1974-09-23 ES ES430317A patent/ES430317A1/en not_active Expired
- 1974-09-23 FR FR7432068A patent/FR2244836B1/fr not_active Expired
- 1974-09-23 NO NO743422A patent/NO139744C/en unknown
- 1974-09-24 DE DE19742445579 patent/DE2445579A1/en active Granted
- 1974-09-24 JP JP49108931A patent/JPS599634B2/en not_active Expired
- 1974-09-24 CH CH1288774A patent/CH603818A5/xx not_active IP Right Cessation
- 1974-09-24 DD DD181286A patent/DD115582A5/xx unknown
- 1974-09-24 TR TR18082A patent/TR18082A/en unknown
- 1974-09-24 FI FI2774/74A patent/FI60038C/en active
- 1974-09-24 CA CA209,867A patent/CA1034080A/en not_active Expired
- 1974-09-24 AR AR255736A patent/AR202842A1/en active
- 1974-09-24 NL NL7412586A patent/NL7412586A/en not_active Application Discontinuation
- 1974-09-24 AT AT769874A patent/AT333789B/en not_active IP Right Cessation
- 1974-09-24 BE BE148855A patent/BE820295A/en not_active IP Right Cessation
- 1974-09-29 IL IL45747A patent/IL45747A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4857899A (en) * | 1971-11-09 | 1973-08-14 |
Also Published As
| Publication number | Publication date |
|---|---|
| SE7411935L (en) | 1975-03-25 |
| FI60038B (en) | 1981-07-31 |
| DE2445579A1 (en) | 1975-04-03 |
| IL45747A (en) | 1977-05-31 |
| CA1034080A (en) | 1978-07-04 |
| FI60038C (en) | 1981-11-10 |
| JPS5077274A (en) | 1975-06-24 |
| AR202842A1 (en) | 1975-07-24 |
| DD115582A5 (en) | 1975-10-12 |
| IL45747A0 (en) | 1974-11-29 |
| NO139744B (en) | 1979-01-22 |
| NO139744C (en) | 1979-05-02 |
| IN142302B (en) | 1977-06-25 |
| NO743422L (en) | 1975-04-21 |
| FR2244836B1 (en) | 1978-11-24 |
| IT1022229B (en) | 1978-03-20 |
| ATA769874A (en) | 1976-04-15 |
| AU7361374A (en) | 1976-04-01 |
| NL7412586A (en) | 1975-03-26 |
| US4013525A (en) | 1977-03-22 |
| BE820295A (en) | 1975-03-24 |
| TR18082A (en) | 1976-09-30 |
| AT333789B (en) | 1976-12-10 |
| CH603818A5 (en) | 1978-08-31 |
| FR2244836A1 (en) | 1975-04-18 |
| DE2445579C2 (en) | 1987-02-05 |
| FI277474A (en) | 1975-03-25 |
| ES430317A1 (en) | 1976-10-01 |
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